Randomly segmented thermoplastic polyurethanes as matrix for electrochemical analysis of Ca.sup.++ ions

Composition, comprising in homogeneous distribution A) at least one salt containing a lipophilic anion, B) a plasticiser-free thermoplastic randomly segmented polyurethane which is soluble in organic solvents, a polyurea or a polyurethane urea, which components are formed from a) 5-45% by weight of an aromatic, cycloaliphatic or linear aliphatic dilsocyanate, b) 0-20% by weight of a linear or branched C2-C12alkylenediol or C2-C12alkylenediamine, c) 0-75% by weight of a polytetrahydrofuran or aminopropyl-terminated polytetrahydrofuran, d) 0-10% by weight of a polyethylene glycol or aminopropyl-terminated polyethylene glycol, e) 0-75% by weight of a polypropylene glycol or aminopropyl-terminated polypropylene glycol, which composition contains f) 15-95% by weight of a hydroxy-, hydroxypropyl- or aminopropyl-terminated polydimethylsiloxane, the percentages relating to the amount of polymer, and the sum of components a) to f) being 100, and C) a nonionic ionophore which forms a complex with Ca++ ions. The invention also relates to an electrode for calcium analysis, containing said composition in the form of a membrane, to a process for the electrochemical analysis of Ca++ ions in solution as well as to the use of this composition for the electrochemical analysis of Ca++ ions.

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Claims

1. A composition, comprising in homogeneous distribution

A) at least one salt containing a lipophilic anion,
B) a plasticiser-free thermoplastic randomly segmented polyurethane which is soluble in organic solvents, a polyurea or a polyurethane urea, which components are formed from
a) 5-45% by weight of an aromatic, cycloaliphatic or linear aliphatic diisocyanate,
b) 0-20% by weight of a linear or branched C.sub.2 -C.sub.12 alkylenediol or C.sub.2 -C.sub.12 alkylenediamine,
c) 0-75% by weight of a polytetrahydrofuran or aminopropyl-terminated polytetrahydrofuran,
d) 0-10% by weight of a polyethylene glycol or aminopropyl-terminated polyethylene glycol,
e) 0-75% by weight of a polypropylene glycol or aminopropyl-terminated polypropylene glycol, which composition contains
f) 15-95% by weight of a hydroxy-, hydroxypropyl- or aminopropyl-terminated polydimethylsiloxane, the percentages relating to the amount of polymer, and the sum of components a) to f) being 100, and
C) a nonionic ionophore which forms a complex with Ca.sup.++ ions.

2. A composition according to claim 1, wherein the aminopropyl-terminated polydimethylsiloxane has a molecular weight of 900 to 4500 dalton.

3. A composition according to claim 1, wherein the alkylenediamine is ethylenediamine, 1,4-diaminobutane or 1,6-diaminohexane.

4. A composition according to claim 1, wherein the aminopropyl-terminated polytetrahydrofuran has a molecular weight of 1000 to 4500 dalton.

5. A composition according to claim 1, wherein the aminopropyl-terminated polyethylene glycol has a molecular weight of 600 to 2000 dalton.

6. A composition according to claim 1, wherein the aminopropyl-terminated polypropylene glycol has a molecular weight of 1000 to 4000 dalton.

7. A composition according to claim 1, comprising in homogeneous distribution

A) at least one salt containing a lipophilic anion,
B) a plasticiser-free thermoplastic randomly segmented polyurethane which is soluble in organic solvents, a polyurea or a polyurethane urea, which components are formed from
a) 5-45% by weight of an aromatic, cycloaliphatic or linear aliphatic diisocyanate,
b) 0-20% by weight of a linear or branched C.sub.2 -C.sub.12 alkylenediol,
c) 0-75% by weight of a polytetrahydrofuran,
d) 0-10% by weight of a polyethylene glycol,
e) 0-75% by weight of a polypropylene glycol, which composition contains
f) 15-95% by weight of a hydroxy-, hydroxypropyl-terminated polydimethylsiloxane, the percentages relating to the amount of polymer, and the sum of components a) to f) being M 100, and
C) a nonionic ionophore which forms a complex with Ca.sup.++ ions.

8. A composition according to claim 1, wherein the nonionic ionophore is an open-chain carbon chain containing several oxygen atoms.

10. A composition according to claim 1, comprising the ionophore in an amount of 0.01 to 10% by weight, based on the amount of polymer.

11. A composition according to claim 10, comprising the ionophore in an amount of 0.1 to 5% by weight, based on the amount of polymer.

12. A composition according to claim 1, wherein the salt containing a lipophilic anion is an alkali metal salt or ammonium salt, and the anion contains unsubstituted or substituted tetraphenylborate.

13. A composition according to claim 12, wherein the cations are Li.sup.+, Na.sup.+, K.sup.+, NH.sub.4.sup.+ and ammonium cations of primary, secondary and tertiary amines as well as quatemary ammonium cations containing 1 to 60 carbon atoms.

14. A composition according to claim 12, wherein the borate anion is tetraphenylborate whose phenyl groups are unsubstituted or substituted by one or more than one C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen or trifluoromethyl.

15. A composition according to claim 14, wherein the borate anion is sodium tetraphenylborate, sodium tetra(3,5-bistrifluoromethylphenyl)borate, potassium tetra(4-chlorophenyl)borate, tetrabutylammoniumtetraphenylborate and tetradodecylammonium(4-chlorophenyl)borate.

16. A composition according to claim 12, wherein the amount of salts containing lipophilic anions is from 0.01 to 10% by weight, based on the amount of polymer.

18. A composition according to claim 7, wherein the hydroxy- or hydroxypropyl-terminated polydimethylsiloxane has a molecular weight of 900 to 4500 dalton.

19. A composition according to claim 7, wherein the alkylenediol is ethylene glycol, 1,4-butanediol or 1,6-hexanediol.

20. A composition according to claim 7, wherein the polytetrahydrofuran has a molecular weight of 1000 to 4500 dalton.

21. A composition according to claim 7, wherein the polyethylene glycol has a molecular weight of 600 to 2000 dalton.

22. A composition according to claim 7, wherein the polypropylene glycol has a molecular weight of 1000 to 4000 dalton.

23. A composition according to claim 7, containing 4,4'-methylenediphenyidiisocyanate in an amount of 15-30% by weight, hydroxypropyl-terminated polydimethylsiloxane in an amount of 25-35% by weight, polytetrahydrofuran in an amount of 35-45% by weight and butanediol in an amount of 1-7% by weight, each based on the amount of the polymer, the sum of the percentages of the individual components being 100.

24. A composition according to claim 7, containing 4,4'-methylenediphenyidiisocyanate in an amount of 8-28% by weight, hydroxypropyl-terminated polydimethylsiloxane in an amount of 70-90% and butanediol in an amount of 0.1-5% by weight, each based on the amount of polymer, the sum of the percentages of the individual components being 100.

25. A composition according to claim 1, wherein the thermoplastic randomly segmented polyurethane, polyurea or polyurethane urea has a molecular weight of 10,000 to 250,000.

26. A composition according to claim 25, wherein the thermoplastic randomly segmented polyurethane, polyurea or polyurethane urea has a molecular weight of 10,000 to 100,000.

27. A composition according to claim 25, wherein the thermoplastic randomly segmented polyurethane, polyurea or polyurethane urea has a molecular weight of 10,000 to 30,000.

28. A composition according to claim 1, wherein the thermoplastic randomly segmented polyurethane, polyurea or polyurethane urea has a glass transition temperature from -125.degree. C. to -40.degree. C.

29. A composition according to claim 1, which is in the form of a membrane.

30. A composition according to claim 29, which is in the form of a self-supporting membrane.

31. A composition according to claim 29, wherein the membrane has a thickness of 50.mu.m to 500.mu.m.

32. An electrode for the analysis of Ca.sup.++ ions, consisting of an outer assembly containing a) an aqueous CaCl.sub.2 solution and an inner reference electrode, or b) a metal wire, the novel composition of claim 1 being applied a) in the form of a membrane or b) as a coating around the metal wire.

33. An electrode for the analysis of Ca.sup.++ ions according to claim 32, wherein the aqueous CaCl.sub.2 solution has a concentration of 0.001 to 0.5 molar.

34. A process for the analysis of Ca.sup.++ ions in solution, which comprises

a) placing the novel composition of claim 1 in the form of a membrane into an electrode or using a metallic wire coated with the composition of claim 1 as electrode,
b) immersing the electrode with the membrane or polymer film in a measuring solution and measuring the electrical voltage difference against a standard electrode.

35. The composition according to claim 1 for use in the electrochemical analysis of Ca.sup.++ ions in solutions.

Referenced Cited
U.S. Patent Documents
4816130 March 28, 1989 Karakelle et al.
5035791 July 30, 1991 Battilotti et al.
Foreign Patent Documents
0125555 November 1984 EPX
62-65216 March 1987 JPX
2086925 May 1982 GBX
Other references
  • Fiedler, U. et al., "Selectrode-The Universal Ion-Selective electrode"Analytica Chimica Acta 67 (1973) 179-193. Oesch, U. et al., "Life Time of Neutral Carrier Based Ion-Selective Liquid-Membrane Electrodes" Anal. Chem. 52 (1980) 692-700. Simon, W. et al., "Calcium-Selective Electrodes" Ann. N.Y. Acad. Sci. 307/52 (1978) 52-69. Database WPI Week 8844, Derwent Publications Ltd., London, GB; AN 88-311565 & JP,A, 63229356 (Agency of Ind. Sci. Tech.) Sep. 26. 1988 (see abstract).
Patent History
Patent number: 5863972
Type: Grant
Filed: Jul 25, 1997
Date of Patent: Jan 26, 1999
Assignee: Chiron Diagnostics Corporation (E. Walpole, MA)
Inventors: Dirk Beckelmann (Saarbrucken), Joseph Berger (Basel)
Primary Examiner: Patrick D. Niland
Attorneys: Arthur S. Morgenstern, Robert P. Blackburn
Application Number: 8/836,370